Electrode materials from hydrous metal and/or hydrous mixed metal oxides

ABSTRACT

An electrode material composed of hydrous metal oxide, such as ruthenium  de, is annealed up to temperature just below the temperature at which the hydrous metal oxide would crystallize. Therefore, the hydrous metal oxide remains amorphous or non-crystalline. A hydrous metal oxide material treated in this manner provides a charge storage capacity and energy density greater than 747 F/g and 92 joules/gram, respectively, over 1 V range in a sulfuric acid electrolyte. This invention also provides a method of material preparation, wherein a sol-gel process is used to fabricate the hydrous metal oxides and wherein commercially available hydrous ruthenium oxide powders are treated and annealed.

GOVERNMENT INTEREST

The invention described herein may be made, used, sold or licensed, byor on behalf of the Government of the United States of America, withoutthe payment to us of any royalties thereon.

DIVISIONAL APPLICATION

This application is a divisional application of U.S. Ser. No.08/678,222, entitled "Electrode Materials From Hydrous Metal and/orHydrous Mixed Metal Oxides And Method Of Preparing The Same." filed Jul.11, 1996, which resulted in U.S. Pat. No. 5,851,506 to be issued on Dec.22, 1998, which was a continuation-in-part of U.S. Ser. No. 08/232,901,with the same title filed by the same inventors herein on Apr. 21, 1994,which parent application is now abandoned. Priority of this parentapplication is claimed.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to electrochemical capacitor electrodes comprisedof materials from hydrous ruthenium oxide, other hydrous metal oxides,or hydrous mixed metal oxides. More particularly, the invention relatesto such electrodes comprised of hydrous ruthenium oxide, or otherhydrous metal oxides, or hydrous mixed metal oxides and toelectrochemical capacitors or electrochemical power sources comprisingsuch electrodes. This invention also relates to a method for thepreparation of fine powders or thick films of such materials at lowtemperatures.

2. Prior Art

Electrochemical capacitors (EC's) are devices which store electricalenergy at the interface between an ionically-conducting electrolytephase and an electronically-conducting electrode material. EC's werefirst described in a 1957 patent by Becker. The first practical deviceswere pioneered by SOHIO as described in U.S. Pat. No. 3,536,963 based onthe double-layer capacitance developed at the interface betweenhigh-area carbon electrodes and sulfuric acid electrolyte solution. Acomplementary system, but originating from a different electrochemicalphenomenon, that is development of pseudocapacitance associated with asurface reaction, was developed by Conway in 1975, in collaboration withContinental Group, Inc. See Can. Pat. by Craig which is listed infra.The materials possessing pseudocapacitance discovered in Conway et al.'swork are metal oxides which include ruthenium oxide (RuO₂), iridiumoxide (IrO₂), cobalt oxide (CoO₂), molybdenum oxide (MoO₂), and tungstenoxide (WO₃). The most effective material discovered was RuO₂ which givesa reversibly accessible pseudocapacitance of many Farads per gram over a1.4 V range.

Heretofore, RuO₂, has been fabricated by the thermal decomposition ofruthenium chloride or hydrous ruthenium chloride. RuO₂, like otherdioxides of the platinum group, e.g. RhO₂, OsO₂, and IrO₂, exhibitsmetallic conductivity and possesses the rutile structure. Thepseudocapacitance, which arises at the RuO₂ and the electrolyteinterface, is due to the facile ionic species absorption on the surfaceof the RuO₂ electrode material.

In order to maximize the charge or energy storage per unit weight ofoxides in this type of system, it is desirable to maximize the surfacearea of the electrode material. Such a maximum BET surface area of 130m² /gram was achieved by Raistrick for optimized processing.

The observed capacitance per unit mass (F/g) and the observedcapacitance per unit area (F/cm), which are determined from the measuredelectrochemical capacitance, the measured surface area, and the knownamount of RuO₂ present in the electrode, are 380 F/g and 200-300 μF/cm²,respectively, in a 1 V range in sulfuric acid electrolyte. Based on theassumption that one H may be adsorbed on each exposed O atom, a chargedensity of 200 μC/cm² is estimated by Raistrick. This suggests that theobserved capacitance 380 F/g is the maximum value that can be achievedfor RuO₂.

These and other references, which are relevant to the present invention,include Can. Pat. No. 1,196,683 issued in 1985 to Craig; U.S. Pat. No.2,800,616 issued in 1957 to Becker; and U.S. Pat. No. 3,536,963 issuedin 1970 to Boos; Conway, Journal of the Electrochemical Society,vol.138, pp. 1539-15, 1991; Raistrick, Proceedings of First Conferenceon Capacitors and Similar Energy Storage Devices, Deerfield Beach, Fla.,Dec. 9-11, 1991, Ansum Enterprises Inc., Boca Raton, Fla.; and U.S. Pat.No. 5,003,428, issued to Shepherd on Mar. 26, 1991.

SUMMARY OF THE INVENTION

Accordingly, one object of the present invention is to provide materialsthat have higher capacitance or higher energy density than that ofruthenium oxide (RuO₂), the highest energy density material availabletoday, for use as an improved electrode material in electrochemicalcapacitors.

Possible applications of such a hydrous ruthenium oxide include thefollowing: electrode material for electrochemical capacitors, oxygen orchlorine evolution anodes, thin film resistors in very large scaleintegrated circuits, or diffusion buffer layers in silicon contactmetallization.

According to the present invention, a new electrode material is formedwhich has an energy density which is more than two times greater thanthe state-of-the-art material, RuO₂. Therefore, the size of thecapacitors and similar applications made of the material of thisinvention will be about half of the present devices. Further, thisinvention provides advantages over prior art, such as:

(1) Ease of material process; and

(2) Smaller capacitor size as a result of higher charge storagecapability.

These objectives and advantages are provided by forming an electrodematerial comprised of hydrous ruthenium oxide which remains amorphous instructure. This material provides a charge storage capacity and energydensity greater than 747 F/g and 92 joules/gram, respectively, over 1 Vrange in a sulfuric acid electrolyte. This invention also provides amethod of material preparation, wherein a sol-gel process is used tofabricate the hydrous metal oxides and wherein commercially availablehydrous ruthenium oxide powders are treated and annealed. Furthermore,the invention also provides a capacitor incorporating the electrodematerial of this invention, which capacitor includes:

(1) an anode (a negative electrode) comprising hydrous ruthenium oxide;

(2) an electrolyte comprising sulfuric acid of various concentration orother electrolytes;

(3) a cathode (a positive electrode) comprising hydrous ruthenium oxide.

Such capacitors having electrodes comprised of hydrous ruthenium oxide(RuO₂.xH₂ O) exhibit an enhanced, linear voltage-charge relationship,excellent reversibility, and long cycle life.

The energy storage mechanism for capacitors made with RuO₂.xH₂ Oelectrodes are mainly fast faradaic reactions occurring between the bulkof the RuO₂.xH₂ O electrode and the electrolyte. It is different withthat of double layer capacitors. The energy storage of double layercapacitors is due to the separation of charges at the interface betweena solid electrode and an electrolyte. The faradaic reaction mechanismbetween the amorphous RuO₂.xH₂ O electrode and the electrolyte is thehydrogenation of the ruthenium oxide, which is similar to that between acrystalline Ru₂ O electrode and the electrolyte. The hydorgenationreaction can be expressed as follows:

    δH.sup.+ +RuO.sub.2 (or RuO.sub.2.xH.sub.2 O)+δe.sup.- H.sub.δ RuO.sub.2 (or H.sub.δ RuO.sub.2.xH.sub.2 O), where 0≦δ≦2                                 Eq. 1

However, for crystalline anhydrous Ru₂ O electrodes, the faradaicreaction can only occur at the surface of the electrode. Therefore, theδ value is less than 1 for crystalline RuO₂ counting every Ru atom inthe material. For the RuO₂.xH₂ O treated under the conditions discoveredby the present inventors, the δ value approaches 2. The energy storagedensity is dependent on the specific surface area of the electrodematerial. For amorphous RuO₂.xH₂ O electrodes made in accordance withthe present invention, however, the faradaic reaction will occur in thewhole bulk of the electrode. Therefore, the energy density of theamorphous RuO₂.xH₂ O electrode will be much higher than that of anyanhydrous crystalline ruthenium oxide electrode.

The H₂ O content, x, in the oxide affects the charge storage capacity.The x value varies between zero and two. The x value decreases as theannealing temperature increases. As shown in FIGS. 3 and 4, the chargestorage capacity increases as the annealing temperature increases.However, the maintenance of the amorphous phase is critical. When thetemperature is high enough, the amorphous phase of the material willconvert to crystalline phase. The charge storage capacity decreasesdramatically as soon as the material becomes crystalline.

The capacitance density of RuO₂.xH₂ O provided by the sol-gel method andproperly treated according to the present invention acheived a valuegreater than 747 farad/gram. A single cell capacitor was fabricated andtested with this new electrode material. The energy storage density ofthe capacitor was greater than 92 joule/gram. These results show clearlythat RuO₂.xH₂ O treated in accordance to the methods of the presentinvention is an excellent electrode material for electrochemicalcapacitors. This material may also be used as electrode material forbatteries and catalyst for fuel cells.

This invention provides methods for preparing the materials with highcharge storage capacity and high energy density. More importantly, thisinvention provides materials with specific qualities irrespective fo thepreparation methods. It is the specific qualities of the materials thatresult in the high charge storage capacity and therefore, high energydensity. The most critical quality of these materials is the amorphousstate of the materials.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other objects of the present invention will be betterunderstood in light of the Detailed Description Of The PreferredEmbodiments and the associated drawings wherein.

FIG. 1 is a plot of X-ray diffraction patterns for RuO₂.xH₂ O preparedby a sol-gel process and annealed at different temperatures.

FIG. 2 is a plot of X-ray diffraction patterns for RuO₂.xH₂ O made fromcommercial powders and annealed at different temperatures.

FIG. 3 is a graph of the specific capacitance of RuO₂.xH₂ O electrodesas a function of the annealing temperature. The RuO₂.xH₂ O electrodeswere prepared by a sol-gel process and were annealed at differenttemperatures. The specific capacitance was calculated based on thecyclic voltammetric measurement. The electrolyte was 0.5 molar solutionof H₂ SO₄.

FIG. 4 is a graph of the specific capacitance of RuO₂.xH₂ O electrodesas a function of the annealing temperature. The RuO₂.xH₂ O electrodeswere made from commercial powders and were annealed at differenttemperatures.

FIG. 5 is a graph of the weight loss as function of the annealingtemperatures. The solid line was measured by a thermogravimetricanalyzer at a temperature scan rate of 10° C./min. The starting materialat 25° C. was Ru(OH)₄ at a quantity of 12.93 mg. The dotted line is thederivative weight loss.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The electrochemical capacitor of this invention includes electrodescomprising hydrous ruthenium oxide, RuO₂.xH₂ O or ruthenium oxide in thehydrous form. The hydrous ruthenium oxide for use in the electrodes ofthe electrochemical capacitor of this invention has properties which aredifferent from those heretofore described in the prior art as forexample in Conway.

In accordance with one method of the present invention, this material,which has a different composition from that of anhydrous rutheniumoxide, is attained by a novel process. In prior art methods, rutheniumoxide, RuO₂, was prepared by decomposing the aqueous ruthenium chloride,RuCl₃, solution at approximately temperatures of 300°-400° C. Incontrast, the process used in this invention involves hydrolyzingruthenium chloride in an aqueous solution, the hydrolysis being promotedby the addition of the hydroxide of sodium, lithium, or ammonia, whichcontrols and stabilizes the pH of the solution. Therefore, the gelformed can be precipitated by then adjusting the pH to higher values.

The above process is also called the sol-gel process. The surface areaof hydrous ruthenium oxides thus formed by the present invention has ofa value as 45 m² /gram or higher. This sol-gel process also allows theformation of films or buffers at low temperatures. The hydrous rutheniumoxide can be further heated and formed with ruthenium oxide attemperatures above 270° C. to have a surface area of 26 m² /gram. Thehydrous ruthenium oxide exhibits electronic properties similar to thoseof ruthenium oxide as well as enhanced ionic properties which allowsadditional charge storage for protons in both the surface and the bulkof the oxides.

Further, the preparation of hydrous ruthenium oxide has been reported.However, the use of hydrous ruthenium oxide for electrochemicalcapacitors has not been reported before. Similarly, the use of otherhydrous metal oxides has not been reported. Of course, as those skilledin the art will recognize, the preparation of other mixed metal oxidesis also known, and therefore, the present invention will also extend toother hydrous metal oxides and hydrous mixed metal oxides. For example,this invention would apply to hydrous metal oxides wherein the metal maybe ruthenium, rhodium, rhenium, osinum or iridium. Moreover, an exampleof a hydrous mixed metal oxide would be Ru_(p) Ti_(q) O₂.xH₂ O whereinp>0 and q>0, and p+q=1, and the precipitate would be a solid solution.Of course, those skilled in art will readily recognize from thisdisclosure that other mixed metals/metals would include cobalt,tungsten, manganese, tantalum, molybdenum, etc. Accordingly, the aboveexample of a hydrous mixed metal oxide Ru_(p) Ti_(q) O₂.xH₂ O whereinp>0 and q>0, and p+q=1, may also be expressed by the general formulaM_(p) M'_(q) O₂.xH₂ O, where p>0 and q>0, and p+q=1, M is a first metalselected from the group of metals consisting of ruthenium, rhodium,rhenium, osmium, and iridium, M' is a second metal selected from thegroup of transition elements consisting of titanium, cobalt, tungsten,manganese, tantalum, molybdenum, iron, and nickel, and, where x is awater content value which is between 0.2 and 1.8, and preferably between0.2 and 1.0. Therefore, it is expected that the hydrous mixed metaloxides will maintain electronic properties similar to those of mixedmetal oxides as well as provide additional charge storage.

In one preferred method of fabricating the new electrode material,RuO₂.xH₂ O is produced from a starting material, RuCl₃.xH₂ O (42% Ru),by a sol-gel process which is described in detail below. Briefly though,the Ru(OH)₄ powder is formed by mixing solutions of RuCl₃.xH₂ O and NaOHto form precipitating powders of Ru(OH)₄. The weight of this precipitateshould measure to be approximately 76% of the weight of the startingmaterial of RuCl₃.xH₂ O. From this weight measurement, it may beinferred that the precipitated powder may be Ru(OH)₄. However, forpurposes of the present invention, it is not important what kindruthenium compound is used at this stage, because this is only anintermediate product. Accordingly, and as those skilled in the art willreadily appreciate, the Ru(OH)₄ can be made with different startingmaterials and reduction agents. For example, the starting materials canbe ruthenium chloride, ruthenium bromide, ruthenium nitrosyl chloride,ruthenium nitrosylnitrate and ruthenium 2,4-pentanedionate. Moreover,the reduction agents can be various alkalies or salts such as NaOH,NaCO₃, NaHCO₃, NaNO₃, KOH, K₂ CO₃, KNO₃, and NH₄ OH, etc.

After the Ru(OH)₄ is produced, then RuO₂.xH₂ O and RuO₂ are formed byheating the Ru(OH)₄ to temperatures of 100° C. and 300° C. respectively.It is critical, however, that the treated powders according to thepresent invention not be subjected to temperatures above 300° C. Theannealing temperature of the present invention is a very importantfactor in determining the specific capacitance of the electrode. Atlower temperatures, i.e. below 200° C., RuO₂.xH₂ O remains in anamorphous state. When the annealing temperature is increased, both theamount of the powders in the crystalline phase and the crystallite sizeincreases. At temperatures above 300° C., the cyrstalline phase ofanhydrous RuO₂ is formed.

FIGS. 1 and 2 show from X-ray diffraction analysis that depending on thesource of the RuO₂.xH₂ O, the crystalline phase of RuO₂.xH₂ O can beobtained between 200° C. and 300° C. FIG. 1 is a plot of X-raydiffraction patterns for RuO₂.xH₂ O prepared by a sol-gel process andannealed at different temperatures. As shown the crystalline peaks beginto form around 175° C. and are well defined at 200° C. for RuO₂.xH₂ Oformed by the sol-gel process of the present invention. However, FIG. 2shows that for RuO₂.xH₂ O made from commercial powders and annealed atdifferent temperatures the crystalline peaks do not form until 300° C.Therefore, depending upon the process used to form the RuO₂.xH₂ O, it iscritical to the present invention that the RuO₂.xH₂ O remain in anamorphous state and the annealing temperature used must not rise abovethe crystalline formation temperature.

Therefore, maximum specific capacitance can be obtained from anelectrode prepared in accordance with the present invention, either fromthe RuO₂.xH₂ O formed by the sol-gel process described in detail belowor from commercially available RuO₂.xH₂ O powders, by annealing eitherpowder at a temperature just below the critical temperature to form thecrystalline phase of the hydrous metal oxide. FIGS. 3 and 4 show graphsof the specific capacitance as a function of annealing temperature forelectrodes made from the sol-gel process (FIG. 3) and commerciallyavailable RuO₂.xH₂ O (FIG. 4). The water content of these materialsexhibits the maximum capacitance value where x is between 0 to 0.5. FIG.3 shows specific capacitance of at least 500 Farads/gram of RuO₂.xH₂ Opowder electrodes made by a sol-gel process, and at annealingtemperatures below 175° C. these powders are amorphous with a watercontent, x, below 2.0. FIG. 3 also shows that when the annealingtemperature is higher than 175° C., the specific capacitance decreasedrapidly to values below 500 Farads/gram because crystalline RuO₂.xH₂ Ostarted to form at the higher temperature. By comparing the resultsbetween the specific capacitance and the crystalline phase as set forthin Table 2 below, it is found that for the electrode with the amorphousphase, the specific capacitance is high, i.e. at least 500 Farads/gram,and increases with the annealing temperature. However, when thecrystalline structure is formed, the specific capacitance of theelectrode decreases rapidly. FIG. 4 demonstrates that when the annealingtemperature exceeds 120° C. the specific capacitance decreased rapidlybelow 500 Farads/gram because crystalline RuO₂.xH₂ O started to form, asdepicted in FIG. 2. Therefore, the maximum value of the specificcapacitance can be obtained at the temperature which is just below thecritical temperature at which the crystalline phase of RuO₂.xH₂ O startsto be formed. As shown a maximum specific capacitance as high as 768 F/gis obtained from an electrode prepared at this optimal annealingtemperature.

                  TABLE 1                                                         ______________________________________                                        Summary of the unique properties of crystalline ruthenium oxide and           amorphous hydrous ruthenium oxide, RuO.sub.2.xH.sub.2 O, where 0.2 < x <      1.8                                                                           ______________________________________                                               RuO.sub.2    RuO.sub.2.xH.sub.2 O, where 0.2 < x < 1.8,                                    preferably 0.2 < x < 1, more preferably                                       when x near 0.5                                           Structure                                                                            Crystalline  Amorphous structure. The water can be                                         removed by heat treatment. The x value                                        decreases with increasing temperature.                                        As soon as the crystalline phase                                              appears, the unique properties of                                             the amorphous hydrous ruthenium                                               oxide disappears.                                         Electrical                                                                           Highly conductive;                                                                         Varies with the water content, x. It is                   properties                                                                           Resistivity ≅6.0x                                                                less conductive when x ≧ 2. It is                         10.sup.-5 ohm-cm                                                                           highly conductive when x ≦ 1.0;                                        Resistivity ≅10.sup.-3 ohm-cm when                                  the x ≦ 1.0.                                       Charge The maximum  Varies with the water content, x.                         storage                                                                              charge storage                                                                             The charge capacity increases with                        capacity                                                                             capacity, c.sub.p, is 380                                                                  decreasing x and reaches its maximum                             F/g for a surface                                                                          value when the material reaches its                              area of 130 m.sup.2 /g.                                                                    critical point where x ≈ 0.5.                            c.sub.p, decreases with                                                                    The highest charge capacity achieved                             decreasing surface                                                                         so far is about 760 F/g which                                    area         is independent of surface area.                           ______________________________________                                    

One specific example of the method of forming RuO₂.xH₂ O according topresent invention is set forth below.

Example of Forming RuO₂.xH₂ O

The Ru(OH)₄ powder is prepared as follows: the required amount ofRuCl₃.nH₂ O (42% wt. Ru) is dissolved in distilled water to give aconcentration of 0.1 mol. At the same time, the NaOH is dissolved indistilled water to a concentration of 0.3 mol. Then, the NaOH solutionis added slowly into the RuCl₃.nH₂ O solution. In this process, the NaOHis employed primarily for the purpose of adjusting and stabilizing thepH at a value of approximately 7, the point at which a controlledprecipitation occurs. During mixing, the RuCl₃.nH₂ O solution isstirred. After stopping the stirring and waiting for a while, it can beseen that Ru(OH)₄ fine powders will precipitate in the NaCl solution.Thus, the process used in this invention involves hydrolyzing rutheniumchloride in an aqueous solution, the hydrolysis being promoted by theaddition of the hydroxide of sodium, lithium, or ammonia, which controlsand stabilizes the pH of the solution. Therefore, the gel formed can beprecipitated by then simply adjusting the pH to higher values withoutthe need of decomposing the aqueous ruthenium chloride, RuCl₃, solutionat approximately temperatures of 300°-400° C., as was previously done inthe prior art.

Ru(OH)₄ fine powders are, then, separated from the NaCl solution by afilter with 8 μm pore size. The hydrolysis product is washed five timesin distilled water by the following procedures: An amount of distilledwater is added into a beaker containing Ru(OH)₄ powders to give aconcentration of 0.2 mol and is stirred with a magnetic stirrer forabout 30 min. Then, the solution is filtered. The dry Ru(OH)₄ powderscan be obtained by drying the precipitate in a vacuum. At this stage,the final fine powders should be Ru(OH)₄ based on the weight change fromthe starting material. However, the final fine powder may be Ru(OH)₃.xH₂O or RuO₂.2H₂ O since the molecular weights of Ru(OH)₄, Ru(OH)₃.xH₂ Oand RuO₂.2H₂ O are so close.

The RuO₂.xH₂ O and RuO₂ are formed by heating Ru(OH)₄ to 100° C. and300° C. in air for about 16 hours, respectively. The weight loss shouldbe approximately 12.5% and 21.5%, respectively. It should be noted,however, that the process of using vacuum to dry Ru(OH)₄, is anunnecessary step for formations of RuO₂.xH₂ O and RuO₂ because they canbe formed by directly heating the wet Ru(OH)₄ to higher temperatures.After forming the RuO₂.xH₂ O, the inventors herein studied variousquality aspect of this material for use in capacitors. From thefollowing, those skilled in the art will readily recognize theadvantages of this material for use in capacitors.

A thermogravimetric analyzer (TGA) was used to study the weight changeduring the thermal processes as shown in FIG. 5. It was found that theweight decreased continually with increasing the temperature up to 300°C. At temperatures above 300° C., the rate of the weight loss was muchlower with increasing the temperature. Two peaks were obtained from aderivation of the TGA curve and appeared at 100° C. and 300° C. Thefirst peak at 100° C. is believed to be due to the formation of RuO₂.xH₂O. The weight change between the first and the second peak is due todehydration process to form RuO₂. The precision weight losses weremeasured for powders after annealing at 100° C. and 300° C. and were12.5% and 21.5%, respectively. These results confirmed the inferencethat RuO₂.xH₂ O and RuO₂ were formed at temperatures of 100° C. and 300°C., respectively. This inference was also confirmed by crystallinestructure measurements shown in FIG. 1.

The crystalline structure of powders was characterized by an X-raydiffractometer. No sharp peaks were obtained from the powder annealed at100° C., which indicates that the RuO₂.xH₂ O is amorphous. From thosepowders annealed at 300° C., three strong x-ray diffractive peaks wereobtained at 28°, 35° and 54° which correspond to (110), (101) and (211)lattice planes of the RuO₂ crystal. See FIG. 1.

From the TGA and the x-ray diffractometer studies, it was found that thetemperature for formation of RuO₂.xH₂ O or RuO₂ are critical. TheRuO₂.xH₂ O may only be formed in the temperature range from 50° C. to200° C., and the crystalline RuO₂ is formed at temperatures higher than200° C. Usually the longer time was needed for the lower temperature tocompletely form above chemical compounds. Combining the results from theTGA, x-ray diffraction, and specific capacitance measurements, it wasalso found that the water content, x, was in the range of 0.2 to 2.0preferably from 0.2 to 1.8, most preferably between 0.2 to 1.0 and theRuO₂.xH₂ O material was of an amorphous phase.

The specific surface areas of RuO₂.xH₂ O and RuO₂ powders weredetermined by the nitrogen absorption measurement and were 44.7 and 26.2m² /gram, respectively. These values are much less than those of carbonbased electrode materials which were widely used for double layercapacitors. It was found that the higher specific surface area ofRuO₂.xH₂ O or RuO₂ can be achieved with the lower concentration of theRuCl₃.xH₂ O and NaOH solutions. It was found that in general thespecific surface area reduces when the annealing temperature isincreased. It was also found that the specific surface area is dependenton the other sample preparation conditions, such as the concentration ofthe RuCl₃.xH₂ O and NaOH solutions, as well as greatly depending on thepH value at which two solutions were mixed. It has been shown that thespecific surface area of the RuO₂ powder is less than that of theRuO₂.xH₂ O powder. This is because the small particles tend to nucleateand to form larger crystalline particles at high temperatures. However,it was also found that that the specific capacitance is insensitive tothe specific surface area for the RuO₂.xH₂ O electrodes made at theoptimal temperature. But for other powders having exhibiting somecrystalline phase, the specific capacitance is strongly dependent on thevalue of the specific surface area.

It is difficult to obtain the resistivity from powder materials.However, pellets of RuO₂.xH₂ O and RuO₂ were made by pressing powdersunder a pressure of 800 Pa. The resistivity of these pellets wasmeasured to be 4.5×10⁻³ Ω-cm and 6.0×10⁻³ Ω-cm, respectively. Thesevalues are at least two orders of magnitude higher than those of bulkmaterials. Nevertheless, the resistivity of the RuO₂.xH₂ O pellet islower than that of the RuO₂ pellet. The high resistivity is mainlycontributed from the contacting resistance between particles. The realresistivity of RuO₂.xH₂ O itself should be much lower than this value.It was demonstrated that highly conductive RuO₂ electrodes could be madeby coating the RuCl₃ solution on the metallic substrate, which is thenthermally decomposed. The highly conductive RuO₂.xH₂ O thin filmelectrode, therefore, can also be achieved.

Further, the resistivity of RuO₂.xH₂ O pellets was also calculated basedon the value of the sheet resistance measured by a standard four probetechnique. These pellets were made by pressing RuO₂.xH₂ O powders at apressure of 8,000 lb/cm². It was found that for RuO₂.xH₂ O powders madeat lower temperatures, the resistivity of the RuO₂.xH₂ O pellet washigher (>10⁻³ Ω-cm). But for RuO₂.xH₂ O powders made at temperatureshigher than 100° C., the resistivity of the RuO₂.xH₂ O pellet isinsensitive to the annealing temperature and was on the order of 10⁻³Ω-cm. The resistivity of the RuO₂.xH₂ O pellet made at the optimaltemperature was about 2-3×10⁻³ Ω-cm. This value is believed to bedominated by the contact resistance of the powders. The bulk resistivityof RuO₂.xH₂ O may be much lower than this value. However, overall theresistivity of the RuO₂.xH₂ O pellets was sufficiently low for use inelectrochemical capacitors.

The capacitance densities of RuO₂.xH₂ O, RuO₂ and carbon black weremeasured by the cyclic voltammetric measurement in the electrolyte of0.5 mol H₂ SO₄. The details of this measurement are described below.From Table 1, it can be seen that the capacitance density of RuO₂.xH₂ Ois the highest one. The most remarkable feature is that the specificcapacitance of RuO₂.xH₂ O is higher than that of RuO₂. As indicated, thehigher capacitance density achieved in this new material is not only dueto the higher surface area but also the intrinsic nature of thematerial. From the cyclic voltammetric curve, two peaks were obtained atpotentials of about 0.4 volt and 0.9 volt versus the saturated calomelelectrode. Therefore, the capacitance developed between this materialand the electrolyte is believed to be predominantly pseudocapacitive.

Capacitance Density

The capacitance densities of carbon black pearls-2000, RuO₂ and RuO₂.xH₂O powders were measured by the cyclic voltammetry. The carbon blackpearls-2000 is commercially available and has the specific surface areaof 1470 m² /gram. Firstly, the carbon black, RuO₂ or RuO₂.xH₂ O powderssoaked in 0.5 mol H₂ SO₄ at the boiling temperature. During themeasurement, the working electrode was made with the electrode materialpasted on the platinum gauze. The counter electrode was a platinumgauze, 80 times as large as the working electrode. The referenceelectrode was a saturated calomel electrode (SCE). The electrolyte, 0.5mol H₂ SO₄ solution, was bubbled with nitrogen gas to avoid theinfluence of dissolved oxygen. The voltammetric curves at 0.5 mV/secwere recorded in the potential range from 0 to 1.0 volt (vs. SCE).Capacitance densities of different electrode materials were averagevalues within the potential range from 0 to 1.0 volt (vs. SCE) and aresummarized in Table 2, which includes surface area, capacitance densityand specific capacitances of carbon black pearls-2000, RuO₂ and RuO₂.xH₂O fine particles. The specific surface area was measured by a nitrogenabsorption method. The capacitance density was measured by a cyclicvoltammetry.

                  TABLE 2                                                         ______________________________________                                                   Specific Surface                                                                           Capacitance                                                                             Specific                                               Area         Density   Capacitance                                 Electrode Material                                                                       (m.sup.2 /gram)                                                                            (farad/gram)                                                                            (μfarad/cm.sup.2)                        ______________________________________                                        Carbon Black                                                                             1475         250        17                                         RuO.sub.2  26.2         200       756                                         RuO.sub.2.xH.sub.2 O                                                                     44.7         747       1671                                        RuO.sub.2.xH.sub.2 O (95%)                                                               --           630       --                                          Teflon (5%)                                                                   ______________________________________                                    

In application, RuO₂.xH₂ O is introduced in a capacitor. For purposes ofthis application single cell capacitors will be described. However, asthose skilled in the art will readily recognize other capacitorapplications will also benefit from the present invention, such as thosementioned in the Summary of the Invention.

For comparison, single cell capacitors were built with two differenttypes of electrodes. The detailed configuration of these capacitors isdescribed below. The energy densities of the two capacitors weremeasured to be 92 J/gram (184 J/cm²) and 68 J/gram (121 J/cm³) for acapacitor using a powder RuO₂.xH₂ O electrode and a capacitor using afilm electrode, respectively. The film electrode contained RuO₂.xH₂ Opowder mixed with 5% teflon. As shown in Table 3, the energy density ofRuO₂.xH₂ O corresponds to capacitance densities of 738 farad/gram for asingle electrode and agrees with the measurement of the cyclicvoltammetry. The most important feature to be noted is that the energydensity of this new material is the highest one available today and isat least two times higher than that reported for RuO₂.

Capacitor Formation

Three types of capacitors were fabricated and tested. The first type wasmade using the powder form of RuO₂.xH₂ O directly as electrodes. TheRuO₂.xH₂ O powder was impregnated with acid solution of 38% weight H₂SO₄ at the boiling temperature. Then, the excess acid solution wasfiltered. The size of each electrode had a diameter of 0.5 inch and athickness of 23 mil. The gravimetric density of the electrode was about2 gram/cm³ for the RuO₂.xH₂ O electrode only. A 2 mil thick tantalumfoil was used as the current collector and a 5 mil thick glass fiberpaper, which was soaked with the acid solution, was used as theseparator. The capacitor was finally sealed by a Teflon™ container. Thesecond type was made using a 5% Teflon™ bonded RuO₂.xH₂ O electrode of athickness about 12 mil. The basic configuration of the capacitor is thesame as the first one.

The electrolyte includes a sulfuric acid of a concentration which variesfrom 0.5 to 4 moles. Other electrolytes including KOH of variousconcentrations, solid polymeric electrolytes (such as Nafion™), andorganic electrolyte may also be employed in this invention.

Capacitances of these two capacitors were measured by a dc charge anddischarge method at a constant current for the voltage range from 0 to 1volt between two electrodes. The capacitance was calculated by thecurrent multiplied by the time of the discharge process which issummarized in Table 3 for the various electrode materials. The energydensities were calculated based on these capacitance values and theoperating voltage of 1 volt. The capacitance densities and the energydensities, measured with dc charge and discharge method are shown inTable 3.

                  TABLE 3                                                         ______________________________________                                                 Capacitance                                                                             Capacitance Energy                                                                              Energy                                   Electrode                                                                              Density   Density     Density                                                                             Density                                  Material (F/g)     (F/cm.sup.3)                                                                              (J/g) (J/cm.sup.3)                             ______________________________________                                        Carbon Black                                                                            82        60         10    7.5                                      RuO.sub.2                                                                              198       542         24.8  68                                       RuO.sub.2.xH.sub.2 O                                                                   738       1475        92.3  184                                      RuO.sub.2.xH.sub.2 O                                                                   540       970         68    121                                      Teflon                                                                        ______________________________________                                    

It must be pointed out that the capacitance or the energy densitiesdescribed in this embodiment are not the maximum values for this newmaterial. For every ruthenium oxide, two hydrogen could be inserted intothe new material as shown in Eq. 1. This suggests that the capacitanceof a value of 1,000 F/g could be achieved with materials according tothe present invention. A lower value of 760 F/g for this new materialachieved in this invention may be due to slight impurities presentduring preparation. Therefore, the higher capacitance and energydensities can be expected for the RuO₂.xH₂ O electrode material.

A third capacitor was built with the RuO₂.xH₂ O powder electrodes whichwere made at the optimal annealing temperature. The electrode materialwas pre-wetted by back filling the electrolyte in a vacuum. 39 weight %of sulfuric acid solution was used as the electrolyte. Two identicalelectrodes separated by a porous membrane with a thickness about 50 μm.The porous membrane was impregnated with the electrolyte. The maximumvoltage which could be applied on a single cell was found to be over onevolt. The energy density was calculated from the dc discharge process ofthe capacitor and was about 96 J/g (or 26.7 Whr/kg) based on the weightof the hydrous ruthenium oxide powders only. This value is consistentwith that calculated from the value of the specific surface area whichis measured by the cyclic voltammogram. The energy deliverableefficiency was estimated from the capacity ratio between the dischargeand charge processes and was over 95%. This third capacitors performancewas also studied at different temperatures. It was found that within thetemperature range from -52° C. to 73° C., the variation of thecapacitance was less than 20%. The cycle life test was also performedfor this capacitor and it was cycled for about 60,000 cycles.

The stability of this new material was also studied by the inventors. Toaccomplish this, a capacitor was built with the powder electrode and wastested under the dc charge and discharge. Until now, this capacitor hasbeen cycled over 4000 times. It was found that the capacitance decayed5% during the first three cycles, since then the capacitance was muchstable and only decayed another 5% until the 4000th cycle. From the dccharge and discharge measurement, the efficiency of the capacitor can beobtained and is higher than 90%.

Although the present invention has been described with regard to threespecific embodiments as to how to manufacture the above identifiedmaterial, those skilled in the art will readily recognize that othervariations of manufacturing this material are available. Accordingly,the inventors do not wish to be limited by the present specification,but only by the appended claims.

What is claimed is:
 1. A capacitor comprising:an anode comprised of anamorphous hydrous metal oxide; an electrolyte; and a cathode comprisedof an amorphous hydrous metal oxide.
 2. The capacitor of claim 1 whereinthe amorphous hydrous metal oxide is comprised of a metal selected fromthe group of metals consisting of ruthenium, rhodium, rhenium, iridium,titanium, cobalt, tungsten, manganese, tantalum, molybdenum, lead, andnickel.
 3. The capacitor, as recited in claim 2, further comprising:saidanode being constructed of a first thin film of said amorphous hydrousmetal oxide on a first substrate; and said cathode being constructed ofa second thin film of said amorphous hydrous metal oxide on a secondsubstrate.
 4. The capacitor, as recited in claim 3, furthercomprising:said amorphous, hydrous metal oxide being ruthenium oxidehaving the formula RuO₂.xH₂ O, where x is a water content value which isbetween 0.2 and 2.0; and a specific capacitance value of at least 500Farads/gram.
 5. The capacitor, as recited in claim 4 wherein said xwater content value is between 0.2 and 1.8;said anode remainingamorphous; and said cathode remaining amorphous.
 6. The capacitor, asrecited in claim 5, wherein said first substrate is nickel.
 7. Thecapacitor, as recited in claim 5, wherein said second substrate isnickel.
 8. The capacitor, as recited in claim 5, further comprising aspecific capacitance value greater than 500 Farads/gram.
 9. A capacitorcomprising:an anode comprised of an amorphous mixed metal oxide; anelectrolyte; and a cathode comprised of an amorphous mixed metal oxide.10. The capacitor, as recited in claim 9, wherein the amorphous mixedmetal oxide is comprised of a metal selected from the group of metalsconsisting of ruthenium, rhodium, rhenium, iridium, titanium, cobalt,tungsten, manganese, tantalum, molybdenum, lead, and nickel.
 11. Thecapacitor, as recited in claim 10, further comprising:said anode beingconstructed of a first thin film of said amorphous mixed metal oxide ona first substrate; and said cathode being constructed of a second thinfilm of said amorphous mixed metal oxide on a second substrate.
 12. Thecapacitor, as recited in claim 11, further comprising:said amorphousmixed metal oxide having the general formula M_(p) M'_(q) O₂.xH₂ O,where p>0 and q>0, and p+q=1, said M is a first metal selected from thegroup of metals consisting of ruthenium, rhodium, rhenium, osmium, andiridium, and said M' is a second metal selected from the group oftransition elements consisting of titanium, cobalt, tungsten, manganese,tantalum, molybdenum, iron, and nickel; where x is a water content valuewhich is between 0.2 and 1.8; and a specific capacitance value of atleast 500 Farads/gram.
 13. The capacitor, as recited in claim 12,wherein said x water content value is between 0.2 and 1.0;said anoderemaining amorphous; and said cathode remaining amorphous.
 14. Thecapacitor, as recited in claim 13, wherein said first substrate isnickel.
 15. The capacitor, as recited in claim 13, wherein said secondsubstrate is nickel.
 16. The capacitor, as recited in claim 13, whereinsaid first substrate is a carbonaceous material.
 17. The capacitor, asrecited in claim 13, wherein said second substrate is a carbonaceousmaterial.
 18. The capacitor, as recited in claim 13, further comprisinga specific capacitance value greater than 500 Farads/gram.